CN103276376A - Method for chemically plating nickel on surface of polymer microsphere - Google Patents
Method for chemically plating nickel on surface of polymer microsphere Download PDFInfo
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- CN103276376A CN103276376A CN2013102360261A CN201310236026A CN103276376A CN 103276376 A CN103276376 A CN 103276376A CN 2013102360261 A CN2013102360261 A CN 2013102360261A CN 201310236026 A CN201310236026 A CN 201310236026A CN 103276376 A CN103276376 A CN 103276376A
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Abstract
The invention provides a method for chemically plating a nano nickel layer with a uniform thickness on the surface of a micron-sized resin microsphere. The micron-sized resin microsphere is a polyacrylic acid special ester microsphere which is provided with an amino or hydroxyl functional group on the surface; a nickel plating technology comprises surface pretreatment, surface activation and chemical plating; a chemical plating solution comprises one, a plurality of or all of nickel salt, a reducing agent, a complexing agent, a stabilizing agent, an accelerating agent, a surface active agent and the like; and mechanical agitation and ultrasonic dispersion are adopted simultaneously in a nickel plating process. The plating layer of the nickel plated microsphere is uniform, firm, smooth in surface, monodispersity is good, and a conductive microsphere meets requirements of an anisotropic conductive film.
Description
Technical field
The present invention relates to plate the uniform nano nickel layer of a layer thickness at the micron order polymer microsphere surface, become conductive micro-balloons.This microballoon mainly is used as the conducting particles of anisotropic conductive film (ACF).ACF is mainly used in being connected of electronic calculator, liquid crystal, plasma body and various semi-conductive display pannel and flexible PCB.
Background technology
The development that information, communication industry are advanced by leaps and bounds drives the electronic circuit board circuit and becomes more meticulous with integrated, and increasing unicircuit need assemble with wiring board, and traditional tin lead welding connects and can not meet the demands.Anisotropic conductive film is that nickel plating/metal/polymer microballoon (particle diameter 1.0 μ m～5.0 μ m) is dispersed in the thermosetting resin, is coated on to form on the thick polyester film of 12.5 μ m.Anisotropic conductive film has been save welding, has simplified technology, has improved reliability, has promoted that greatly electronics develops to light, thin, little direction.At present anisotropic conductive film has been widely used in being connected of liquid-crystal display and flexible PCB.
The technological core of anisotropic conductive film is the preparation of the micron order list dispersed electro-conductive microballoon of uniform particle diameter.The preparation of conductive micro-balloons is to prepare the monodispersed polymer microsphere of uniform particle diameter of micron level by traditional polymerization methods as letex polymerization, suspension polymerization etc. earlier, and then plates the nickel dam of one deck nano thickness at polymer microsphere surface.Wherein the polymer microsphere among the present invention adopts the mode of suspension polymerization, used monomer contains functional groups such as amino or hydroxyl, the polymer microsphere that obtains like this is to contain aerobic or nitrogen-atoms isoreactivity functional group, in ensuing electroless plating, easy and the inorganic metal-salt of these active function groups is affine, thereby solved (JP58-106554 in the patent in the past, JP63-191818, CN200810015180.5) use vinylbenzene, polymerizations such as Vinylstyrene do not contain the active function groups that has affinity with metal level later on, and the polymer microsphere surface that causes plates inorganic metal level, bonding force is not firm, the difficult problem that coating comes off easily.The particle size range of this polymer microsphere is at the 1-50 micron.
The nickel dam that plates one deck nano thickness at polymer microsphere surface has similar patent 97121929.X200510019313.2, and 200610068708.6, but coating is not firm, rough, and the microballoon monodispersity is poor.The present invention adopts the polymer microsphere that contains functional group as mother bulb, and electroless plating adopts combined oxidation reduction nickel-plating liquid, under mechanical stirring and hyperacoustic acting in conjunction, obtain nickel coating evenly, firmly, smooth surface, monodispersity is good, reaches the conductive micro-balloons that anisotropic conductive film requires.
Summary of the invention
The making method that is used for the micron order resin microsphere plating nickel on surface complex microsphere of anisotropic conducting film, at first preparation contains the micron order polymer microsphere of active function groups, secondly is to plate the uniform nano metal layer of a layer thickness on the surface.
The used monomer of micron order polymer microsphere of preparation band functional group is the extraordinary ester microsphere of polyacrylic acid that contains amino or hydroxy functional group, comprises picture polymethyl acrylic acid amino ethyl ester, poly hydroxy ethyl acrylate, polymethyl acrylic acid dimethylamino ethyl ester, polyacrylate and amino ethyl ester, Poly(Hydroxyethyl Methacrylate), polyacrylic acid dimethylamino ethyl ester, polymethyl acrylic acid 3-chlorine 2-hydroxy propyl ester etc.Polymerization process is that the monomer of described formula ratio, dispersion agent, mixed solvent are joined in the four-necked bottle, after stirring forms homogeneous system, feeds nitrogen purge, adds the monomer that is dissolved with initiator.Keep nitrogen atmosphere and suitable stirring velocity, 70 ℃ of following polyreaction 16～24h.With sample ultracentrifuge centrifugal settling, discard supernatant liquid, with washing with alcohol lower floor microballoon, centrifuge washing is repeatedly.Microballoon vacuum-drying 24h in vacuum drying oven with after the washing namely gets product.
It is by microsphere surface pre-treatment, surface active that polymer microsphere surface plates the uniform nano metal layer of layer thickness process, adopts the redox nickel-plating liquid to plate the uniform metal nickel dam of one deck 1-100 nanometer under mechanical stirring and ultrasonication.
Wherein the redox nickel-plating liquid has comprised a kind of, several or whole in nickel salt, reductive agent, buffer reagent, complexing agent, stablizer, promotor, the tensio-active agent etc.Nickel salt comprises single nickel salt, nickelous nitrate, nickelous chloride etc.; Reductive agent comprises reductive agents commonly used such as Sulfothiorine, ferrous ammonium sulphate; The purpose of buffer reagent is to keep the PH of plating bath, when preventing nickel plating owing to separate out the decline of the caused pH value of hydrogen ion in a large number.The effect that adds complexing agent is to allow complexing agent and metal ion carry out complexing, the concentration of reduction free metal ion, the height degree also stable.Organic acid and salt thereof are as complexing agent.Function of stabilizer is to prevent that plating bath from being polluted, and solid particulate, the loading capacity that has a catalytic activity is excessive or too small, pH value is crossed under the high abnormal conditions, and chemical plating fluid can spontaneous reaction and the situation of the rapid decomposition failure of plating bath is taken place.Complexing agent is ethylenediamine tetraacetic acid (EDTA), trolamine.Stablizer mainly contains lead nitrate, Potassium Iodate.Add the sedimentation rate that small amounts of promoters can improve coating in plating bath, promotor commonly used has: alanine, aminobutyric acid, aspartic acid.Adding tensio-active agent is in order to improve the coating slickness, to improve the dispersiveness of plating ball.SPAN-80, TWEN, OP-10 etc. are arranged.
Embodiment
Example one
The four neck flasks that reaction vessel uses 250mL band polytetrafluoro to stir, logical water of condensation is used N
2Thermometer is inserted in protection.Use heating in water bath.Methacrylic acid amino ethyl ester: 10g; Polyvinylpyrrolidone K90:0.8g; AIBN:0.1g; Ethanol: 150.With N
2Entrance is inserted into the following displaced air 1h of liquid level, and then mentions gas phase and continue logical N
2Be warming up to 70 ℃, stirring velocity 80 commentaries on classics/min, polymerization 22h.With washing with alcohol three times, filtration under diminished pressure, product vacuum-drying.The resulting polymers microspherulite diameter is 4.0 μ m.
Example two
The four neck flasks that reaction vessel uses 250mL band polytetrafluoro to stir, logical water of condensation is used N
2Thermometer is inserted in protection.Use heating in water bath.Methacrylic acid 3-chlorine 2-hydroxy propyl ester: 10g; PVPK30:0.8g; AIBN:0.1g; Ethanol 50g; Methyl alcohol: 50g; Ethylene glycol monomethyl ether: 50g.With N
2Entrance is inserted into the following displaced air 1h of liquid level, and then mentions gas phase and continue logical N
2Be warming up to 70 ℃, stirring velocity 80 commentaries on classics/min, polymerization 20h.With washing with alcohol three times, filtration under diminished pressure, product vacuum-drying.The resulting polymers microspherulite diameter is 8.0 μ m.
Example three
The particle diameter that example one is obtained is that 4.0 μ m polymer microspheres, 5 grams are through surface preparation, surface active, ultrasonic 2min in 100ml methyl alcohol; Add 3ml sodium polyacrylate, 4.5ml polyethylene glycol 6000,6ml Sodium dodecylbenzene sulfonate, 0.6ml thiocarbamide, add the 300ml nickel-plating liquid.Nickel-plating liquid is composed as follows:
Single nickel salt (NiSO
46H
2O): 40g/L
Inferior sodium phosphate (NaH
2PO
2H
2O): 45g/L
Trisodium Citrate (Na
3C
6H
5O
72H
2O): 100g/L
Ammonium chloride (NH
4C): 55g/L
Trolamine (C
6H
15NO
3): 50g/L
Alanine: 0.5g/L
OP-10：0.3g/L
pH＝8.5
Mixture is transferred in the 500ml four-hole port grinding bottle, and four-hole bottle is placed band heating in water bath ultrasound reactor, 50 ℃ of bath temperatures, stirring velocity 150r/min, dropping ammonia makes pH keep 8.5, reaction times 45min.Vacuum filtration, washing, alcohol is washed, and gets solid 7.5g.The electron microscopic observation microballoon, microsphere features smooth surface, no projection, monodispersity is better, nickel dam mean thickness 65nm.
Example four
The particle diameter that example one is obtained is that 4.0 μ m polymer microspheres, 5 grams are through surface preparation, surface active, ultrasonic 2min in 100ml methyl alcohol; Add 3ml sodium polyacrylate, 4.5ml polyethylene glycol 6000,6ml Sodium dodecylbenzene sulfonate, 0.6ml thiocarbamide, add the 300ml nickel-plating liquid.Nickel-plating liquid is composed as follows:
Single nickel salt (NiSO
46H
2O): 40g/L
Inferior sodium phosphate (NaH
2PO
2H
2O): 45g/L
Trisodium Citrate (Na
3C
6H
5O
72H
2O): 100g/L
Ammonium chloride (NH
4C): 55g/L
Trolamine (C
6H
15NO
3): 50g/L
Alanine: 0.5g/L
Potassium Iodate: 1.0g/L
OP-10：0.3g/L
pH＝8.5
Mixture is transferred in the 500ml four-hole port grinding bottle, and four-hole bottle placed band heating in water bath ultrasound reactor, 55 ℃ of bath temperatures, stirring velocity 150r/min, open ultrasonic dispersing simultaneously, ultrasonic power is 2400w, reaction times 45min, obtain microsphere features smooth surface, no projection, the better nickel plating ball of monodispersity, nickel dam mean thickness 80nm.
Example five
The particle diameter that example two is obtained is that 8.0 μ m polymer microspheres, 5 grams are through surface preparation, surface active, ultrasonic 2min in 100ml methyl alcohol; Add 3ml sodium polyacrylate, 4.5ml polyethylene glycol 6000,6ml Sodium dodecylbenzene sulfonate, 0.6ml thiocarbamide, add the 300ml nickel-plating liquid.Nickel-plating liquid is composed as follows:
Single nickel salt (NiSO
46H
2O): 40g/L
Inferior sodium phosphate (NaH
2PO
2H
2O): 45g/L
Trisodium Citrate (Na
3C
6H
5O
72H
2O): 100g/L
Ammonium chloride (NH
4C): 55g/L
Trolamine (C
6H
15NO
3): 50g/L
Alanine: 0.5g/L
Potassium Iodate: 1.0g/L
OP-10：0.3g/L
pH＝8.5
Mixture is transferred in the 500ml four-hole port grinding bottle, and four-hole bottle placed band heating in water bath ultrasound reactor, 65 ℃ of bath temperatures, stirring velocity 200r/min, open ultrasonic dispersing simultaneously, ultrasonic power is 3000w, reaction times 60min, obtain microsphere features smooth surface, no projection, the better nickel plating ball of monodispersity, nickel dam mean thickness 78nm.
Example six
The particle diameter that example two is obtained is that 8.0 μ m polymer microspheres, 5 grams are through surface preparation, surface active, ultrasonic 2min in 100ml methyl alcohol; Add 3ml sodium polyacrylate, 4.5ml polyethylene glycol 6000,6ml Sodium dodecylbenzene sulfonate, 0.6ml thiocarbamide, add the 300ml nickel-plating liquid.Nickel-plating liquid is composed as follows:
Nitric acid nickel (NO
3)
2: 40g/L
Inferior sodium phosphate (NaH
2PO
2H
2O): 45g/L
Trisodium Citrate (Na
3C
6H
5O
72H
2O): 100g/L
Ammonium chloride (NH
4C): 55g/L
Trisodium phosphate (Na
4P
2O
710H
2O): 45g/L
Ethylenediamine tetraacetic acid (EDTA): 50g/L
Lead nitrate: 0.2g/L
SPAN-80：0.4g/L
pH＝10.0
Mixture is transferred in the 500ml four-hole port grinding bottle, and four-hole bottle is placed band heating in water bath ultrasound reactor, 65 ℃ of bath temperatures, stirring velocity 200r/min,, open ultrasonic dispersing simultaneously, ultrasonic power is 3000w, reaction times 60min.
Obtain microsphere features smooth surface, no projection, the nickel plating ball that monodispersity is good, nickel dam mean thickness 90nm.
Claims (6)
1. a making method that is used for the micron order resin microsphere chemical nickel plating on surface of anisotropic conducting film is characterized in that: plate the uniform nano metal layer of a layer thickness at the micron order polymer microsphere surface.
2. polymer microsphere according to claim 1 is the extraordinary ester microsphere of polyacrylic acid that the surface has amino or hydroxy functional group, comprises picture polymethyl acrylic acid amino ethyl ester, poly hydroxy ethyl acrylate, polymethyl acrylic acid dimethylamino ethyl ester, polyacrylate and amino ethyl ester, Poly(Hydroxyethyl Methacrylate), polyacrylic acid dimethylamino ethyl ester, polymethyl acrylic acid 3-chlorine 2-hydroxy propyl ester etc.
3. the diameter of the extraordinary ester microsphere of polyacrylic acid according to claim 2 is the 1-50 micron.
4. according to claim 1, it is the uniform metal nickel dam of 1-100 nanometer that microsphere surface plates a layer thickness.
5. according to claim 4, the nickel plating technology of employing is redox nickel plating.Nickel plating technology is surface preparation, surface active and electroless plating.The mode that adopts mechanical stirring, ultra-sonic dispersion or mechanical stirring and ultra-sonic dispersion to carry out simultaneously in the electroless plating process, temperature of reaction are 40 ℃-70 ℃; Reaction times is 30min-60min.
6. according to claim 5, comprised a kind of, several or whole in nickel salt, reductive agent, complexing agent, stablizer, promotor, the tensio-active agent etc. in the used plating bath of electroless plating.Nickel salt comprises single nickel salt, nickelous nitrate, nickelous chloride etc.; Reductive agent comprises reductive agents commonly used such as Sulfothiorine, ferrous ammonium sulphate.Complexing agent is ethylenediamine tetraacetic acid (EDTA), trolamine.Stablizer mainly contains lead nitrate, Potassium Iodate.Promotor commonly used has: alanine, aminobutyric acid, aspartic acid.Tensio-active agent has SPAN, TWEN, OP-10 etc.
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| CN2013102360261A CN103276376A (en) | 2013-06-14 | 2013-06-14 | Method for chemically plating nickel on surface of polymer microsphere |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114457325A (en) * | 2021-12-30 | 2022-05-10 | 安徽中科元贞科技有限责任公司 | Method for controlling thickness of nickel layer of nickel-plated polymer microsphere |
| CN114807912A (en) * | 2022-05-10 | 2022-07-29 | 常州德创高新材料科技有限公司 | Method for chemically plating nickel on surface of poly glycidyl methacrylate microsphere |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186820A (en) * | 1997-11-21 | 1998-07-08 | 天津大学 | High molecular composite conductive micro-balloons |
| US20090014321A1 (en) * | 2005-04-04 | 2009-01-15 | Commissariat A L'energie Atomique | Surface Treatment Electrode |
| CN102176337A (en) * | 2011-01-06 | 2011-09-07 | 天津大学 | Composite conductive particles for anisotropic conductive film and preparation method |
| CN102977395A (en) * | 2012-12-11 | 2013-03-20 | 苏州纳微生物科技有限公司 | Preparation method of conductive material-made composite microsphere |
| CN102990062A (en) * | 2012-12-17 | 2013-03-27 | 苏州纳微生物科技有限公司 | Method for preparing composite microsphere |
-
2013
- 2013-06-14 CN CN2013102360261A patent/CN103276376A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186820A (en) * | 1997-11-21 | 1998-07-08 | 天津大学 | High molecular composite conductive micro-balloons |
| US20090014321A1 (en) * | 2005-04-04 | 2009-01-15 | Commissariat A L'energie Atomique | Surface Treatment Electrode |
| CN102176337A (en) * | 2011-01-06 | 2011-09-07 | 天津大学 | Composite conductive particles for anisotropic conductive film and preparation method |
| CN102977395A (en) * | 2012-12-11 | 2013-03-20 | 苏州纳微生物科技有限公司 | Preparation method of conductive material-made composite microsphere |
| CN102990062A (en) * | 2012-12-17 | 2013-03-27 | 苏州纳微生物科技有限公司 | Method for preparing composite microsphere |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114457325A (en) * | 2021-12-30 | 2022-05-10 | 安徽中科元贞科技有限责任公司 | Method for controlling thickness of nickel layer of nickel-plated polymer microsphere |
| CN114457325B (en) * | 2021-12-30 | 2023-12-08 | 安徽中科元贞科技有限责任公司 | Nickel layer thickness control method for nickel-plated high polymer microspheres |
| CN114807912A (en) * | 2022-05-10 | 2022-07-29 | 常州德创高新材料科技有限公司 | Method for chemically plating nickel on surface of poly glycidyl methacrylate microsphere |
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Application publication date: 20130904 |